CN102339980B - Positive pole and the lithium battery comprising this positive pole - Google Patents

Positive pole and the lithium battery comprising this positive pole Download PDF

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Publication number
CN102339980B
CN102339980B CN201110198639.1A CN201110198639A CN102339980B CN 102339980 B CN102339980 B CN 102339980B CN 201110198639 A CN201110198639 A CN 201110198639A CN 102339980 B CN102339980 B CN 102339980B
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active material
sublayer
general formula
ground floor
positive pole
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CN102339980A (en
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李淳律
崔益圭
金荣基
宋在爀
李泳勋
宋有美
金润昶
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/006—Compounds containing, besides molybdenum, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249923—Including interlaminar mechanical fastener

Abstract

The invention discloses a kind of positive pole and the lithium battery comprising this positive pole.Described positive pole comprises the ground floor of collector, irreversibly de-embedding lithium ion and permission lithium ion reversibly embeds and the second layer of de-embedding.In one embodiment, described ground floor comprises the first sublayer and the second sublayer further, and wherein said first sublayer is between described collector and described second sublayer.Described first sublayer comprises general formula 1Li 2mo 1-nr 1 no 3the first active material represented, and described second sublayer comprises general formula 2Li 2ni 1-mr 2 mo 2the second active material represented.In general formula 1,0≤n < 1, and R 1be selected from the group be made up of the combination of manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn), magnesium (Mg), nickel (Ni) and aforementioned elements.In general formula 2,0≤m < 1, and R2 is selected from the group be made up of the combination of Mn, Fe, Co, Cu, Zn, Mg, molybdenum (Mo) and aforementioned elements.

Description

Positive pole and the lithium battery comprising this positive pole
Technical field
The disclosure relates to positive pole and comprises the lithium battery of this positive pole.
Background technology
Converts chemical energy is become electric energy by the electrochemical redox reaction between chemical substance by lithium battery.Conventional lithium battery comprises positive pole, negative pole and electrolyte.
Recently, along with electronic installation requires high-performance day by day, the battery for these devices also needs high power capacity and high-power output.In order to provide the battery with high power capacity, the active material of high power capacity or high battery charging voltage can be needed.Such as, the silicon class composite material with high power capacity can be used as the negative electrode active material of battery cathode.But, silicon class composite material irreversibly de-embedding lithium.
Summary of the invention
One or more execution mode of the present invention comprises the positive pole with new construction and the lithium battery comprising described positive pole.
Other side will part be set forth in the following description, and partly will become obvious by specification, or understand by the enforcement to provided execution mode.
According to one or more execution mode of the present invention, positive pole comprises: collector; The irreversibly ground floor of de-embedding lithium ion; The second layer with de-embedding is reversibly embedded with permission lithium ion.
Described ground floor and the second layer are arranged on described collector successively by this order.Described ground floor can comprise the first active material represented by following general formula 1:
General formula 1:Li 2mo 1-nr 1 no 3.
In general formula 1,0≤n < 1, and R 1be selected from the group be made up of the combination of manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn), magnesium (Mg), nickel (Ni) and aforementioned elements.
Described ground floor can comprise the second active material represented by following general formula 2:
General formula 2:Li 2ni 1-mr 2 mo 2
In general formula 2,0≤m < 1, and R 2be selected from the group be made up of the combination of manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn), magnesium (Mg), molybdenum (Mo) and aforementioned elements.
Described ground floor can comprise the first active material represented by following general formula 1 and the second active material represented by following general formula 2:
General formula 1:Li 2mo 1-nr 1 no 3general formula 2:Li 2ni 1-mr 2 mo 2
In general formula 1,0≤n < 1, and R 1be selected from the group be made up of the combination of at least two kinds of manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn), magnesium (Mg), nickel (Ni) and aforementioned elements.In general formula 2,05m < 1, and R 2be selected from the group be made up of the combination of at least two kinds of Mn, Fe, Co, Cu, Zn, Mg, molybdenum (Mo) and aforementioned elements.Described second active material can comprise Li further 2ni 8o 10phase.
Described ground floor can comprise the first sublayer and the second sublayer, and wherein said first sublayer is inserted between described collector and described second sublayer.Described first sublayer comprises the first active material represented by above general formula 1, and described second sublayer comprises the second active material represented by above general formula 2.Described second active material can comprise Li further 2ni 8o 10phase.
Described ground floor can comprise the first sublayer and the second sublayer, and wherein said first sublayer is between described collector and described second sublayer.Described first sublayer comprises the second active material represented by above general formula 2.Described second sublayer comprises the first active material represented by above general formula 1.Described second active material can comprise Li further 2ni 8o 10phase.
According to the one or more execution mode of the present invention, lithium battery comprises: the negative pole comprising negative electrode active material; Positive pole, described positive pole comprises: the ground floor of collector, irreversibly de-embedding lithium ion and allow lithium ion reversibly to embed and the second layer of de-embedding; And electrolyte.The positive pole of described lithium battery can have above-mentioned same characteristic features.
Described negative electrode active material can comprise the material being selected from the group be made up of the combination of at least two kinds of silicon, silicon class composite material (such as Si oxide), tin, tin class composite material, lithium titanate and these materials.
Accompanying drawing explanation
By reference to the accompanying drawings, these and/or other side be will become more apparent by the explanation of following execution mode and are more readily understood, wherein:
Fig. 1 is the schematic cross-section of the positive pole according to embodiment of the present invention;
Fig. 2 comprises Li 2ni 8o 10the Li of phase 2niO 2x-ray diffraction (XRD) analysis chart of class active material;
Fig. 3 is the schematic cross-section of the positive pole according to another execution mode of the present invention;
Fig. 4 is the schematic cross-section of the lithium battery structure illustrated according to embodiment of the present invention; And
Fig. 5 is the cycle life curve chart of the lithium battery manufactured according to comparative example 1 and embodiment 1,5 and 6.
Embodiment
Now be described in detail to execution mode, some of them are shown in the drawings, and wherein in full text, similar Reference numeral refers to similar element.In this respect, current disclosed execution mode can have different forms and should not be construed to claim is restricted to listed in the text those.Therefore, each execution mode is described to explain each aspect of the present invention, characteristic sum characteristic.
According to each execution mode, positive pole comprises collector, ground floor and the second layer.Ground floor comprises one or more materials of irreversibly de-embedding lithium ion.The second layer comprises permission lithium ion and reversibly embeds one or more materials with de-embedding.In some embodiments, ground floor and the second layer can stack gradually on a current collector by this order.Or, in other embodiments, ground floor and the second layer can reverse order on a current collector stacking.
Fig. 1 is the schematic cross-section of the positive pole 10 according to embodiment of the present invention.With reference to Fig. 1, positive pole 10 comprises collector 11, ground floor 13 and the second layer 15.Ground floor 13 is arranged on collector 11, and irreversibly de-embedding lithium ion.The second layer 15 is arranged on ground floor 13, and allows lithium ion reversibly to embed and de-embedding.
Collector 11 can be any one in the group being selected from and being made up of Copper Foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, the polymeric substrates scribbling conducting metal and aluminium base.But, the collector of other form any can be used to substitute.Or, collector 11 can be manufactured by the mixture of material listed above or by being stacked on another by the substrate be made up of above-mentioned material one.According to each execution mode, collector 11 can have any one in various structures.
In each execution mode, ground floor 13 can irreversibly de-embedding lithium ion.Such as, battery initial charge or to carry out between charge period (that is, during positive pole first time provides lithium ion to negative pole), ground floor 13 de-embedding lithium ion also provides lithium ion to negative pole.But the interdischarge interval after initial charge, ground floor 13 does not allow Lithium-ion embeding.In other words, ground floor 13 does not participate in the charge-discharge cycles of battery.But the second layer 15 allows lithium ion reversibly to embed and de-embedding, and participates in the charge-discharge cycles of battery.
Therefore, if the positive pole comprising ground floor 13 and the second layer 15 with comprise and can use together with the negative pole of the irreversibly negative electrode active material of de-embedding lithium ion, ground floor 13 can compensate the irreversibility of negative pole, thus can improve the capability retention of lithium battery.This is supported by following explanation.
Such as, let us considers lithium battery L1, and it comprises the positive pole (allow lithium ion reversibly embed and de-embedding) be only made up of the second layer 15 and the negative pole be made up of negative electrode active material (can de-embedding 80% receives from positive pole during initial charge lithium ion).If the second layer 15 is de-embedding 100 lithium ions during initial charge, the interdischarge interval of negative pole after initial charge can de-embedding 80 lithium ions in theory.
Meanwhile, in order to compare, let us considers lithium battery L2, and it is identical with lithium battery L1, is can the ground floor 13 of irreversibly de-embedding 20 lithium ions during its positive pole is included in initial charge further.Then, positive pole can provide 120 lithium ions (instead of 100 lithium ions) to negative pole during initial charge.Therefore, the interdischarge interval of negative pole after initial charge can de-embedding 96 (=120 × 0.8) individual lithium ion in theory.In other words, the use of ground floor 13 in the positive pole of lithium battery L2 can compensate the irreversibility of negative pole.Thus, lithium battery L2 while basic maintenance capacity identical with lithium battery L1, can have good capability retention.
In each execution mode, ground floor 13 can comprise the first active material represented by following general formula 1:
General formula 1Li 2mo 1-nr 1 no 3
In general formula 1,0≤n < 1, and R 1be selected from the group be made up of the combination of manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn), magnesium (Mg), nickel (Ni) and these elements.
Such as, above-mentioned first active material can be Li 2moO 3the class active material compound of general formula 1 (namely as n=0).Term " Li used in literary composition 2moO 3class active material " refer to and comprise Li 2moO 3the material of compound.Li 2moO 3class active material can comprise further and having and Li 2moO 3compound chemistry measures different layers and/or phase.In addition, term used in literary composition " ... class active material " can be understood in a similar manner.First active material can be can the material of irreversibly de-embedding lithium ion.
Or ground floor 13 can comprise the second active material represented by following general formula 2:
General formula 2:Li 2ni 1-mr 2 mo 2
In general formula 2,0≤m < 1, and R 2be selected from the group be made up of the combination of Mn, Fe, Co, Cu, Zn, Mg, molybdenum (Mo) and these elements.
Second active material can be Li 2niO 2class active material.Li 2niO 2class active material also can be can the material of irreversibly de-embedding lithium.
When ground floor 13 comprises above-mentioned second active material, the second active material, such as Li 2niO 2class active material, can comprise Li further 2ni 8o 10phase.
Second active material, such as Li 2niO 2class active material, can irreversibly release a large amount of lithium ion, and can produce gas.Such as, according to reaction 1, as the Li of the second active material 2niO 2class active material can produce O 2:
Reaction 1:Li 2niO 2→ NiO+O+2Li
The Li produced by the product of reaction 1 2o can generate Li with one or more components of electrolyte, conductive agent and/or various additive reaction 2cO 3, then Li 2cO 3cO can be released 2.
As mentioned above, the second active material, such as Li 2niO 2class active material, can irreversibly de-embedding lithium ion, and its can produce O in lithium battery 2and/or CO 2.
Such as, if Li 2niO 2class active material comprises Li further 2ni 8o 10phase, the then phase of Absorbable organic halogens second active material, and the side reaction of product that can suppress or substantially stop reaction 1.Thus, this comprises such as Li 2niO 2class active material can the irreversibly a large amount of lithium ion of de-embedding as the ground floor 13 of the second active material, and can suppress or substantially stop to produce O 2and/or CO 2side reaction, thus improve the stability of positive pole.
Li 2ni 8o 10by regulating or controlling for the synthesis of the second active material as Li 2niO 2the heat-treat condition of class active material obtains.Such as, by Li 2o and NiO stoichiometrically mixes than (1: 1 mol ratio), and by gained mixture at inert atmosphere conditions (such as N 2atmosphere) under at one or more temperature (such as about 550 DEG C) of about 500 DEG C to 600 DEG C heat treatment about 5 little of about 15 hours (such as about 10 hours).Heat treated material can be cooled to the temperature within the scope of room temperature to 100 DEG C.Then, by gained material at inert atmosphere conditions (such as N 2atmosphere) under at one or more temperature (such as about 550 DEG C) of about 500 DEG C to 600 DEG C further heat treatment about 5 little of about 15 hours (such as about 10 hours), provide and comprise Li 2ni 8o 10the Li of phase 2niO 2class active material.
Fig. 2 is Li 2niO 2the figure that the X-ray diffraction (XRD) of class active material is analyzed, this Li 2niO 2class active material passes through at N 2atmosphere, the Li of heat treatment stoichiometric proportion (1: 1 mol ratio) at 550 DEG C 2o and NiO mixture 10 hours, then further heat treatment preparation in 10 hours at 550 DEG C.Fig. 2 confirms Li 2ni 8o 10the existence of phase.
In some embodiments, ground floor 13 can comprise both the first active material and the second active material.
Although the second active material is as Li 2niO 2class active material produces O by the product reacting 1 2, but the first active material is as Li 2moO 3class active material irreversibly de-embedding lithium ion simultaneously stability O 2.In other words, although O 2can be released by the second active material, but the first active matter mass-energy absorbs the O produced by the second active material 2, thus substantially can stop the clean generation of gas in lithium battery.
When ground floor 13 comprises the first active material (such as Li 2moO 3class active material) and the second active material (such as Li 2niO 2class active material) the two time, the second active material can comprise Li further 2ni 8o 10phase.In this case, reaction 1 even can be suppressed, and more producible a small amount of O in lithium battery 2can by the first material absorbing.Therefore, can the irreversibility of effective compensation negative pole, and the stability of lithium battery can be improved.
The thickness of ground floor 13 can change according to various factors, and these factors comprise the material of ground floor 13, the desired structure of lithium battery, the positive active material etc. that will use.In each execution mode, ground floor 13 can have the thickness of about 2 μm to about 30 μm.In each execution mode, ground floor 13 can have the thickness of about 5 μm to about 15 μm.
The second layer 15 can allow lithium ion reversibly to embed and de-embedding.Active material for the second layer 15 can be and allows lithium ion reversibly to embed any suitable positive active material for lithium battery with de-embedding.Such as, the second layer 15 can comprise any one in following positive active material.But, any suitable positive active material can be used.
Li aa 1-bx bd 2, wherein 0.95≤a≤1.1, and 0≤b≤0.5; Li ae 1-bx bo 2-cd c, wherein 0.95≤a≤1.1,0≤b≤0.5, and 0≤c≤0.05; LiE 2-bx bo 4-cd c, wherein 0≤b≤0.5, and 0≤c≤0.05; Li ani 1-b-cco bb cd α, wherein 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05, and 0 < α≤2; Li ani 1-b-cco bx co 2-αm α, wherein 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05, and 0 < α < 2; Li ani 1-b-cco bx co 2-αm 2, wherein 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05, and 0 < α < 2; Li ani 1-b-cmn bx cd α, wherein 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05, and 0 < α≤2; Li ani 1-b-cmn bx co 2-αm α, wherein 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05, and 0 < α < 2; Li ani 1-b-cmn bx co 2-αm 2, wherein 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05, and 0 < α < 2; Li ani be cg do 2, wherein 0.90≤a≤1.1,0≤b≤0.9,0≤c≤0.5, and 0.001≤d≤0.1; Li ani bco cmn dg eo 2, wherein 0.90≤a≤1.1,0≤b≤0.9,0≤c≤0.5,0≤d≤0.5,0≤e≤0.1; Li aniG bo 2, wherein 0.90≤a≤1.1, and 0.001≤b≤0.1; Li acoG bo 2, wherein 0.90≤a≤1.1, and 0.001≤b≤0.1; Li amnG bo 2, wherein 0.90≤a≤1.1, and 0.001≤b≤0.1; Li amn 2g bo 4, wherein 0.90≤a≤1.1, and 0≤b≤0.1; QO 2; QS 2; LiQS 2; V 2o 5; LiV 2o 5; LiZO 2; LiNiVO 4; Li (3-f)j 2(PO 4) 3, wherein 0≤f≤2; Li (3-f)fe 2(PO 4) 3, wherein 0≤f≤2; LiFePO 4; And lithium titanate.
In above general formula, A is selected from by nickel (Ni), cobalt (Co), manganese (Mn) and the group that forms thereof; X is selected from the group be made up of aluminium (Al), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), strontium (Sr), vanadium (V), rare earth element and combination thereof; D is selected from by oxygen (O), fluorine (F), sulphur (S), phosphorus (P) and the group that forms thereof; E is selected from by cobalt (Co), manganese (Mn) and the group that forms thereof; M is selected from by fluorine (F), sulphur (S), phosphorus (P) and the group that forms thereof; G is selected from by aluminium (Al), chromium (Cr), manganese (Mn), iron (Fe), magnesium (Mg), lanthanum (La), cerium (Ce), strontium (Sr), vanadium (V) and the group that forms thereof; Q is selected from by titanium (Ti), molybdenum (Mo), manganese (Mn) and the group that forms thereof; Z is selected from by chromium (Cr), vanadium (V), iron (Fe), scandium (Sc), yttrium (Y) and the group that forms thereof; And J is selected from by vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu) and the group that forms thereof.
The second layer 15 can comprise and being selected from by LiCoO 2, LiMn 2o 4, LiFePO 4, at least one compound in the group that forms of the compound to be represented by following general formula 3 and the compound that represented by following general formula 4.But, any other suitable active material can be used to replace.
General formula 3Li x(Ni pco qmn r) O y
General formula 4Li nni t1co t2al t3o m
In general formula 3,0.95≤x≤1.05,0 < p < 1,0 < q < 1,0 < r < 1, p+q+r=1, and 0 < y≤2.In general formula 4,0.95≤n≤1.05,0 < t1 < 1,0 < t2 < 1,0 < t3 < 1, t1+t2+t3=1, and 0 < m≤2.In general formula 3 and 4, x, p, q, r, y, n, t1, t2, t3 and m represent the mol ratio of each element.
Such as, 0.97≤x≤1.03, p can be 0.5, q and can be 0.2, r and can be 0.3, and y can be 2.But x, p, q, r and y can appropriate changes.Such as, the active material of general formula 3 can be LiNi 0.5co 0.2mn 0.3o 2compound.But, any suitable active material according to general formula 3 can be used.
Such as, in general formula 4, t1=t2=t3.But t1, t2 and t3 can appropriate changes.Such as, in the active material of general formula 4, n=1, m=2 and t1=t2=t3.
Ground floor 13 can be about 5: 95 to about 30: 70 with the Thickness Ratio of the second layer 15.Such as, ground floor 13 can be about 5: 95 to about 20: 80 with the Thickness Ratio of the second layer 15.But the thickness of these two layers is adjustable as any suitable ratio.Consider the structure etc. of positive active material used, required lithium battery, ground floor 13 suitably can change with the Thickness Ratio of the second layer 15 in aforementioned range.
Fig. 3 is the schematic cross-section of the positive pole 20 according to another execution mode.With reference to Fig. 3, positive pole 20 comprises collector 21, ground floor 23, the second layer 25.Ground floor 23 is arranged on collector 21, and irreversibly de-embedding lithium ion.The second layer 25 is arranged on ground floor 23, and allows lithium ion reversibly to embed and de-embedding.Collector 21 and the second layer 25 is all applicable in conjunction with the detailed description of above Fig. 1 to collector 11 and the second layer 15.
Ground floor 23 can comprise the first sublayer 23A and the second sublayer 23B.As shown in the figure, the first sublayer 23A is between collector 21 and the second sublayer 23B, and the second sublayer 23B is between the first sublayer 23A and the second layer 25.
First sublayer 23A can comprise the first active material represented by following general formula 1.Second sublayer 23B can comprise the second active material represented by general formula 2.
General formula 1Li 2mo 1-nr 1 no 3
General formula 2Li 2ni 1-mr 2 mo 2
In general formula 1,0≤n < 1, and R 1be selected from the group be made up of the combination of at least two kinds of Mn, Fe, Co, Cu, Zn, Mg, Ni and aforementioned elements.In general formula 2,0≤m < 1, and R 2be selected from the group be made up of the combination of at least two kinds of Mn, Fe, Co, Cu, Zn, Mg, Mo and aforementioned elements.
Above-mentioned first active material can be Li 2moO 3class active material.Above-mentioned second active material can be Li 2niO 2class active material.But any other suitable material can be used for the first and second active materials.Second sublayer 23B can comprise such as can the second active material of the irreversibly a large amount of lithium ion of de-embedding.As mentioned above, the second active material can produce O 2.But, owing to comprising the first active material as Li 2moO 3first sublayer 23A Absorbable rod O of class active material 2, therefore can suppress or stop the O that the second sublayer 23b produces 2clean generation.Therefore, the irreversibility of negative pole can be compensated by ground floor 23, thus the capability retention improvement that can obtain lithium battery and stability guarantee.
In each execution mode, the second active material such as Li 2niO 2class active material can comprise Li further 2ni 8o 10phase.In some embodiments, the first sublayer 23A can comprise the second active material as Li 2niO 2class active material, and the second sublayer 23B can comprise the first active material as Li 2moO 3class active material.The second active material in first sublayer 23A can comprise Li further 2ni 8o 10phase.
The Thickness Ratio of the first sublayer 23A and the second sublayer 23B can change according to various factors, and these factors comprise the performance level etc. needed for active material, lithium battery.Such as, the Thickness Ratio of the first sublayer 23A and the second sublayer 23B can be about 5: 95 to about 95: 5.Such as, the Thickness Ratio of the first sublayer 23A and the second sublayer 23B can be about 75: 25 to about 25: 75.
Below positive pole is described in more detail.Although describe positive pole with reference to the non-limiting embodiment of Fig. 1 and Fig. 3, positive pole can have any one in various structures.
According to each execution mode, lithium battery comprises: the negative pole comprising negative electrode active material; Collector; Comprise the positive pole of at least one positive active material; And electrolyte.In each execution mode, positive pole comprises the ground floor of irreversibly de-embedding lithium ion, and allows lithium ion reversibly to embed the second layer with de-embedding.
In each execution mode, the optional adaptive multiple negative electrode active material for lithium battery of negative electrode active material.Such as, this negative electrode active material can be the negative electrode active material with high power capacity.Such as, negative electrode active material can be the material with high power capacity, but irreversibly de-embedding lithium ion.
The example of negative electrode active material comprises the combination of at least two kinds of silicon, silicon class composite material, tin, tin class composite material, lithium titanate or these materials.But, any other suitable material can be used to replace.
For example, negative pole can comprise silicon thin film or silicon class composite material.Silicon class composite material can comprise silicon and at least one non-silicon material and/or element.Such as, silicon class composite material is selected from by Si oxide, silicon-graphite composite material, Si oxide-graphite composite material, silico-carbo nanometer tube composite materials, Si oxide-carbon nano tube compound material and is expressed as Si-M 1material, wherein M 1be selected from the group be made up of the combination of at least two kinds in Al, Sn, Ag, Fe, Bi, Mg, Zn, In, Ge, Pb, Ti and these elements.But, any other suitable material can be used to replace.
In the silicon thin film with high power capacity or silicon class composite material, when lithium salts decomposed in the electrolytic solution in charging and discharging cycle period, lewis acid can be produced, as PF 5or HF, and lewis acid can destroy Si-Si bond and irreversibly form Si-F key.Si-F key has strong adhesion, and stable, thus in negative pole, produce irreversible reaction.
For example, tin class composite material is selected from by tin-graphite composite material, tin-carbon nanometer tube composite material and Sn-M 2the group of the material composition represented, wherein M 2be selected from the group be made up of the combination of at least two kinds of Al, Si, Ag, Fe, Bi, Mg, Zn, In, Ge, Pb, Ti and these elements.But, any other suitable material can be used to replace.
The example of lithium titanate comprises the lithium titanate of the lithium titanate of spinel structure, anatase structured lithium titanate and ramsdellite structure, and they are classified according to its crystal structure.
Such as, negative electrode active material can be Li 4-xti 5o 12(0≤x≤3).Such as, negative electrode active material can be Li 4ti 5o 12.But, any other suitable material can be used to replace.
Similar to silicon based thin film or silicon class composite material, tin, tin class composite material and lithium titanate have high power capacity, but irreversibly de-embedding lithium ion, thus capability retention can be caused poor.
But if having high power capacity but the negative pole of capability retention difference is used from lithium battery with the positive pole one comprising ground floor, this lithium battery can have high capacity characteristics and good capability retention.This is because the ground floor of positive pole provides the lithium ion of irreversibly de-embedding to negative pole.Above-mentioned ground floor can be implemented in a variety of manners.According to the execution mode of ground floor, the pure qi (oxygen) body in lithium battery produces and can significantly be stoped or reduce, and lithium battery can have the stability of improvement.
Such as, the negative pole that can use together with above-mentioned positive pole can comprise the silicon composite (such as Si oxide) as negative electrode active material.But, any other suitable negative electrode active material can be used to replace.
Electrolyte can comprise non-aqueous organic solvent and lithium salts.Non-aqueous organic solvent in electrolyte can play the effect of the Ion transfer medium of the electrochemical reaction participating in lithium battery.The example of non-aqueous organic solvent comprises carbonate-based solvent, esters solvent, ether solvent, ketones solvent, alcohols solvent and aprotic solvent.
The example of carbonate-based solvent comprises dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonic acid ester (EPC), methyl ethyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate (BC).But, any other suitable carbonate-based solvent can be used to replace.
The example of esters solvent comprises methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton (GBL), decalactone, valerolactone, mevalonolactone and caprolactone.But, any other suitable esters solvent can be used to replace.
The example of ether solvent comprises dibutyl ethers, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethoxy-ethane, 2-methyltetrahydrofuran and oxolane.But, any other suitable ether solvent can be used to replace.
The example of ketones solvent is cyclohexanone.But, any other suitable ketones solvent can be used to replace.
The example of alcohols solvent comprises ethanol and isopropyl alcohol.But, any other suitable alcohols solvent can be used to replace.
The example of aprotic solvent comprises nitrile, and (such as R-CN, wherein R is C 2-C 20straight chain, side chain, maybe can comprise the aromatic ring of double bond bonding or the cyclic hydrocar-bons part of ehter bond), acid amides (such as dimethyl formamide), dioxolanes (such as DOX) and sulfolane.But, any other suitable aprotic solvent can be used to replace.
Non-aqueous organic solvent can comprise the combination of single solvent or at least two kinds of solvents be used alone.If use solvent combination, the ratio of non-aqueous organic solvent can change according to the desired properties of lithium battery, and this is apparent to those of ordinary skill in the art.
Such as, non-aqueous organic solvent can be volume ratio be about 3: 7 ethylene carbonate (EC) and methyl ethyl carbonate (EMC).Such as, the mixture of non-aqueous organic solvent can be volume ratio be EC, GBL and EMC of about 3: 3: 4.
Lithium salts in electrolyte to be dissolved in non-aqueous organic solvent and to play lithium ion source in lithium battery, and accelerates the lithium ion mobility between positive pole and negative pole.
Such as, lithium salts can comprise and being selected from by LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiN (SO 2c 2f 5) 2, Li (CF 3sO 2) 2n, LiC 4f 9sO 3, LiClO 4, LiAlO 2, LiAlCl 4, LiN (C xf 2x+1sO 2) (C yf 2y+1sO 2) (wherein x and y is independently natural number separately), LiCl, LiI and LiB (C 2o 4) 2at least one supporting electrolyte salt in the group that (di-oxalate lithium borate or LiBOB) forms.In each execution mode, electrolyte salt can be the combination of two or more of aforementioned electrolyte salt.
The concentration of lithium salts can in the scope of about 0.1M to about 2.0M.Such as, the concentration of lithium salts can be about 0.6M to about 2.0M.When the concentration of lithium salts is within the scope of these, electrolyte can have desirable conductance and viscosity, thus lithium ion can effective mobility.
Electrolyte can comprise the additive that can improve lithium battery cryogenic property further.This example additives comprises carbonates material and propane sultone (propanesulton, PS).But, any suitable additive can be used.In addition, a kind of additive can be used, or the combination of additive can be used.
The example of above-mentioned carbonates material comprises ethylene carbonate (VC); Have and be selected from by halogen atom (as F, Cl, Br and I), cyano group (CN) and nitro (NO 2) at least one substituent ethylene carbonate (VC) derivative in the group that forms; And have and be selected from by halogen atom (as F, Cl, Br and I), cyano group (CN) and nitro (NO 2) at least one substituent ethylene carbonate (EC) derivative in the group that forms.But, any suitable carbonates material can be used.
Electrolyte can comprise at least one additive in the group being selected from and being made up of ethylene carbonate (VC), fluoroethylene carbonate (FEC) and propane sultone (PS) further.
Based on the non-aqueous organic solvent of 100 weight portions and the total amount of lithium salts, the amount of additive can be about 10 weight portions or less.Such as, based on the non-aqueous organic solvent of 100 weight portions and the total amount of lithium salts, the amount of additive can in the scope of about 0.1 weight portion to about 10 weight portions.When the amount of additive is within the scope of this, lithium battery can have the low-temperature characteristics of improvement satisfactorily.
Such as, based on the non-aqueous organic solvent of 100 weight portions and the total amount of lithium salts, the amount of additive can in the scope of about 1 weight portion to about 5 weight portions.Based on the non-aqueous organic solvent of 100 weight portions and the total amount of lithium salts, the amount of additive can in the scope of about 2 weight portions to about 4 weight portions.
Such as, based on the non-aqueous organic solvent of 100 weight portions and the total amount of lithium salts, the amount of additive can be about 2 weight portions.
According to each execution mode of lithium battery, dividing plate can between positive pole and negative pole.Any dividing plate being usually used in lithium battery can be used.In one embodiment, dividing plate can have lower resistance to the Ion transfer in electrolyte and have high electrolyte reserve capability.Examples of materials for the formation of dividing plate comprises glass fibre, polyester, teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) and combination thereof, and each in them can be nonwoven or textile fabric.In one embodiment, the dividing plate reeled formed by the such as material such as polyethylene and polypropylene can be used for lithium ion battery.In another embodiment, the dividing plate that can retain a large amount of organic electrolyte can be used for lithium ion polymer battery.These dividing plates can be prepared according to following methods.
Mixed polymerization resin, filler and solvent are to prepare baffle combination thing.Then, baffle combination thing can directly be coated on electrode, then dry formation barrier film.Or baffle combination thing may be cast on independent carrier, then drying forms baffle combination thing film, is removed and be laminated to electrode by this baffle combination thing film to form barrier film from carrier.
Fluoropolymer resin can be any material being commonly used for battery lead plate binding agent.The example of fluoropolymer resin comprises vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate and composition thereof.But, any suitable fluoropolymer resin can be used.Such as, can use and comprise about 8 to the vinylidene fluoride/hexafluoropropylene copolymer of the hexafluoropropylene of about 25wt%.
Fig. 4 is the perspective diagram of the lithium battery 30 according to one embodiment of the present invention.With reference to Fig. 4, lithium battery 30 comprises the electrode assemblie with positive pole 23, negative pole 22 and the dividing plate between positive pole 23 and negative pole 22 24.Electrode assemblie is contained in battery case 25, and potted component 26 sealed cell shell 25.Electrolyte (not shown) is injected battery case 25 with impregnated electrode assembly.Lithium battery 30 is by overlieing one another successively to form lamination by positive pole 23, dividing plate 24 and negative pole 22, and reel this lamination the lamination this rolled insert in battery case 25 and manufacture.
The type of lithium battery is not particularly limited, and can be such as lithium secondary battery, as lithium ion battery, lithium ion polymer battery, lithium-sulfur cell etc., or is lithium primary cell.
Now in detail the method manufacturing lithium battery will be described.Positive pole is by forming first and second layers on a current collector to manufacture.Such as, form the method for ground floor to comprise the first active material represented by general formula 1 and/or the second active material represented by general formula 2 and binding agent and solvent to prepare ground floor composition.Then, ground floor composition is directly coated on collector (such as aluminium collector) to form ground floor.Subsequently, by comprise allow lithium ion reversibly embed with the coating of the second layer composition of the active material of de-embedding, binding agent and solvent on the first layer, then dry to form the second layer, thus manufacture positive plate.Or, respectively the first and second layer compositions are cast on independent carrier, to form first and second layers, then they are separated with carrier and lamination on a current collector to manufacture positive plate.The limiting examples of suitable solvent comprises 1-METHYLPYRROLIDONE, acetone, water etc.
Or, the first sublayer composition, the second sublayer composition and second layer composition can be prepared respectively, and be coated with successively on a current collector to form the first sublayer, the second sublayer and the second layer respectively.Illustrate in greater detail the active material joined in these compositions above.
Binding agent in first and second layers is used for active material particle being bonded together and being bonded to collector.The limiting examples of binding agent comprises polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, Carboxylation polyvinyl chloride, polyvinyl fluoride, the polymer comprising oxirane, PVP, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene butadiene rubbers (SBR), the SBR of propylene acidifying, epoxy resin and nylon.
Ground floor and/or the second layer can comprise the conductive agent for providing conductivity to positive pole further.Any other electrically conductive material that can not cause chemical change in the battery can be used.The example of conductive agent can comprise carbonaceous material, as native graphite, Delanium, carbon black, acetylene black, Ketjen black, carbon fiber etc.; With the metal group material of powder or fibers form, as copper (Cu), nickel (Ni), aluminium (Al), silver (Ag) etc.; And electric conducting material, comprise conducting polymer as polypheny lene derivatives and composition thereof.
Collector can be aluminium (Al).But, any other suitable material can be used to replace.
Similarly, negative electrode active material, conductive agent, binding agent and solvent is mixed to prepare composition of cathode active materials.This composition of cathode active materials is directly coated on collector (such as Cu collector), or be cast in form negative electrode active material plasma membrane on independent carrier, then this negative electrode active material plasma membrane be separated with carrier and be laminated on Cu collector to obtain negative plate.At this, the amount of negative electrode active material, conductive agent, binding agent and solvent can be amount conventional in lithium battery.According to each execution mode, negative pole can with any one manufacture in plating or multiple method.
Conductive agent in composition of cathode active materials, binding agent and solvent are identical with used those in positive electrode active compound composition.If needed, plasticizer can be added to produce hole in battery lead plate to each of positive electrode active compound composition and composition of cathode active materials further.
Dividing plate between positive plate and negative plate with formed with after through winding or folding battery component.Then this initial component is loaded in cylindrical or rectangular battery shell.Then inject the electrolyte into battery case, thus complete the manufacture of lithium battery pack.
Embodiment
embodiment 1
By negative electrode active material SiO in 1-METHYLPYRROLIDONE solvent xwith polyvinylidene fluoride (PVDF) binding agent with 90: 10 weight ratio mixing to prepare cathode size.This cathode size is coated on copper (Cu) paper tinsel, to be formed, there is the thin negative plate of 14 μm of thickness, and at 135 DEG C dry 20 minutes to provide negative pole.
By Li 2moO 3active material, PVDF binding agent and carbonaceous conductive agent are dispersed in 1-METHYLPYRROLIDONE solvent with the weight ratio of 96: 2: 2 to prepare ground floor composition.Ground floor composition is coated on to form the thin pole plate with 60 μm of thickness on aluminium (Al) paper tinsel, and dry 20 minutes at 135 DEG C (comprise Li to form the ground floor with 35 μm of thickness 2moO 3active material).
By LiCoO 2active material, PVDF binding agent and carbonaceous conductive agent are dispersed in 1-METHYLPYRROLIDONE solvent with the weight ratio of 96: 2: 2 to prepare second layer composition.The coating of second layer composition is had the thin pole plate of 60 μm of thickness to be formed on the first layer, and at 135 DEG C dry 3 hours or more of a specified duration, the second layer that then repressed formation has 35 μm of thickness (comprises LiCoO 2active material), thus complete the manufacture of positive pole.
Mixture (volume ratio is 3: 7) to ethylene carbonate (EC) and methyl ethyl carbonate (EMC) adds 1.0MLiPF 6to prepare electrolyte.
Assembling negative pole, positive pole, electrolyte and porous polyethylene (PE) barrier film are to manufacture Coin shape monocell.
embodiment 2
Manufacture lithium battery in the same manner as example 1, just in ground floor composition, use Li 2niO 2replace Li 2moO 3.The ground floor of lithium battery comprises Li 2niO 2active material.
embodiment 3
Manufacture lithium battery in the same manner as example 1, just use in ground floor composition and comprise Li 2ni 8o 10the Li of phase 2niO 2replace Li 2moO 3.The ground floor of lithium battery comprises containing Li 2ni 8o 10the Li of phase 2niO 2active material.
Comprise Li 2ni 8o 10the Li of phase 2niO 2active material synthesis is as follows.At N 2under atmosphere, by the Li of stoichiometric proportion (1: 1 mol ratio) 2the heat treatment 10 hours at 550 DEG C of O and NiO mixture, then further heat treatment 10 hours at 550 DEG C.Fig. 2 is Li 2niO 2the figure that the X-ray diffraction (XRD) of active material is analyzed.
embodiment 4
Manufacture lithium battery in the same manner as example 1, just add further in ground floor composition and comprise Li 2ni 8o 10the Li of phase 2niO 2.The ground floor of this lithium battery comprises containing Li 2ni 8o 10the Li of phase 2niO 2and Li 2moO 3.Comprise Li 2ni 8o 10the Li of phase 2niO 2and Li 2moO 3weight ratio be about 75: 25.
embodiment 5
Manufacture lithium battery in the same manner as example 1, just form the first sublayer and the second sublayer successively to obtain ground floor, replace the ground floor according to embodiment 1.By Li 2moO 3active material, PVDF binding agent and carbonaceous conductive agent (acetylene black, the DENKABLACK) weight ratio with 96: 2: 2 are dispersed in 1-METHYLPYRROLIDONE solvent with the composition for the preparation of the first sublayer.First sublayer composition is coated on to form the thin pole plate with 60 μm of thickness on aluminium (Al) paper tinsel, and dry 3 hours or more of a specified duration at 135 DEG C have the first sublayer of 35 μm of thickness with formation.By Li 2niO 2active material, PVDF binding agent and carbonaceous conductive agent (acetylene black, the DENKABLACK) weight ratio with 96: 2: 2 are dispersed in 1-METHYLPYRROLIDONE solvent with the composition for the preparation of the second sublayer.Second sublayer composition is coated on to form the thin pole plate with 60 μm of thickness on the first sublayer, and dry 3 hours or more of a specified duration at 135 DEG C have the second sublayer of 35 μm of thickness with formation.
embodiment 6
Manufacture lithium battery in the same manner as example 1, just form the first sublayer and the second sublayer successively to obtain ground floor, replace the ground floor according to embodiment 1.By Li 2niO 2active material, PVDF binding agent and carbonaceous conductive agent (acetylene black, the DENKABLACK) weight ratio with 96: 2: 2 are dispersed in 1-METHYLPYRROLIDONE solvent to prepare the first sublayer composition.First sublayer composition is coated on to form the thin pole plate with 60 μm of thickness on aluminium (Al) paper tinsel, and dry 3 hours or more of a specified duration at 135 DEG C have the first sublayer of 35 μm of thickness with formation.By Li 2moO 3active material, PVDF binding agent and carbonaceous conductive agent (acetylene black, the DENKABLACK) weight ratio with 96: 2: 2 are dispersed in 1-METHYLPYRROLIDONE solvent to prepare the second sublayer composition.Second sublayer composition is coated on to form the thin pole plate with 60 μm of thickness on the first sublayer, and dry 3 hours or more of a specified duration at 135 DEG C have the second sublayer of 35 μm of thickness with formation.
comparative example 1
Manufacture lithium battery in the same manner as example 1, be just different from embodiment 1, do not form ground floor.
the evaluation of embodiment
The lithium battery of comparative example 1 and embodiment 1,5 and 6 is placed 20 hours under room temperature (25 DEG C), then carries out the charging and discharging (formation process) of lithium battery with the multiplying power of 0.05C.After formation process completes, these lithium batteries are charged with constant current/constant voltage (CC/CV) pattern with the charge cutoff electric current of the charging voltage of the multiplying power of 0.6C, 4.35V and 0.06C, then discharges with the discharge cut-off voltage of the multiplying power of 1C and 2.5V.Repeat the circulation of this charging and discharging with the capacity and the 0.6C/1C cycle life that measure each lithium battery.This 0.6C/1C cycle life is determined as the relative capacity percentage relative to total initial cycle capacity.The results are shown in Fig. 5.With reference to Fig. 5, the lithium battery of embodiment 1,5 and 6 shows life characteristic more better than the lithium battery of comparative example 1.
As mentioned above, according to above one or more execution mode of the present invention, even if use the negative pole comprising the negative electrode active material of irreversibly de-embedding lithium ion, the lithium battery comprising above-mentioned positive pole according to each execution mode also can have good capacity maintenance characteristics and stability.
It should be understood that the illustrative embodiments illustrated in literary composition only should be interpreted as illustration purpose, instead of in order to limit.Feature in usual each execution mode or the explanation of aspect are interpreted as can be used for other similar characteristics in other execution modes or aspect.

Claims (9)

1. a positive pole, comprising:
Collector;
The irreversibly ground floor of de-embedding lithium ion; With
Lithium ion is allowed reversibly to embed the second layer with de-embedding;
Wherein, described ground floor and the second layer are arranged on described collector successively by this order, and the Thickness Ratio of described ground floor and the second layer is 5:95 to 30:70;
Wherein, described ground floor comprises the first active material represented by following general formula 1 and/or the second active material represented by following general formula 2:
General formula 1:Li 2mo 1-nr 1 no 3,
Wherein, in general formula 1,0≤n<1, and R 1be selected from the group be made up of the combination of at least two kinds of Mn, Fe, Co, Cu, Zn, Mg, Ni and aforementioned elements;
General formula 2:Li 2ni 1-mr 2 mo 2,
Wherein, in general formula 2,0≤m<1, and R 2be selected from the group be made up of the combination of at least two kinds of Mn, Fe, Co, Cu, Zn, Mg, Mo and aforementioned elements.
2. positive pole according to claim 1, wherein, described ground floor comprises the second active material represented by general formula 2, and described ground floor comprises Li further 2ni 8o 10phase.
3. positive pole according to claim 1, wherein, described ground floor comprises the first sublayer and the second sublayer, described first sublayer is between described collector and described second sublayer, described first sublayer comprises the first active material represented by described general formula 1, and described second sublayer comprises the second active material represented by described general formula 2.
4. positive pole according to claim 3, wherein, described second sublayer comprises Li further 2ni 8o 10phase.
5. positive pole according to claim 1, wherein, described ground floor comprises the first sublayer and the second sublayer, described first sublayer is between described collector and described second sublayer, described first sublayer comprises the second active material represented by described general formula 2, and described second sublayer comprises the first active material represented by described general formula 1.
6. positive pole according to claim 5, wherein, described first sublayer comprises Li further 2ni 8o 10phase.
7. a lithium battery, comprising:
Comprise the negative pole of negative electrode active material;
Positive pole in claim 1 to 6 described in any one; And
Electrolyte.
8. lithium battery according to claim 7, wherein, described negative electrode active material comprises the material in the group being selected from and being made up of the combination of at least two kinds of silicon, silicon class composite material, tin, tin class composite material, lithium titanate and these materials.
9. lithium battery according to claim 8, wherein, described negative electrode active material comprises Si oxide.
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